1. Field of the Invention
This invention relates to catalyst systems, both supported and unsupported, and to a process using such catalyst systems for the production of high molecular weight polymers, particularly polyolefins. The catalyst systems comprise a monocyclopentadienyl transition metal compound, an alumoxane, and a modifier. The catalyst system is highly active, at low ratios of aluminum to the transition metal, hence catalyzes the production of a polyolefin product containing low levels of catalyst metal residue.
2. Description of the Related Art
As is well known, various processes and catalysts exist for the homopolymerization or copolymerization of olefins. For many applications it is of primary importance for a polyolefin to have a high weight average molecular weight while having a relatively narrow molecular weight distribution. A high weight average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-.alpha.-olefin copolymer with high strength properties.
Traditional Ziegler-Natta catalyst systems--a transition metal compound cocatalyzed by an aluminum alkyl--are capable of producing polyolefins having a high molecular weight but the polyolefins produced thereby are generally of a broad molecular weight distribution.
More recently a catalyst system has been developed wherein the transition metal compound has two or more cyclopentadienyl ring ligands--such transition metal compound being referred to as a metallocene--which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of a Group IV B metal, particularly, titanocenes and zirconocenes, have been utilized as the transition metal component in such "metallocene" containing catalyst system for the production of polyolefins and ethylene-.alpha.-olefin copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl--as is the case with a traditional type Ziegler-Natta catalyst system--the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.
It has since become known that such metallocenes may be cocatalyzed with an alumoxane--rather than an aluminum alkyl--to provide a metallocene catalyst system of high activity for the production of polyolefins. A metallocene-alumoxane catalyast system generally produces polyolefins of a narrow molecular weight distribution.
The zirconium metallocene species, as cocatalyzed or activated with an alumoxane, are commonly more active than their hafnium or titanium analogous for the polymerization of ethylene alone or together with an .alpha.-olefin comonomer. When employed in a non-supported form--i.e., as a homogeneous or soluble catalyst system--to obtain a satisfactory rate of productivity even with the most active zirconium species of metallocene typically requires the use of a quantity of alumoxane activator sufficient to provide an aluminum atom (Al) to transition metal atom (TM) ratio (Al:TM) of at least greater than 1000:1; often greater than 5000:1, and frequently on the order of 10,000:1. Such quantities of alumoxane impart to a polymer produced with such catalyst system an undesirable content of catalyst metal residue, i.e., an undesirable "ash" content (the nonvolatile metal content). In high pressure polymerization procedures using soluble catalyst systems wherein the reactor pressure exceeds about 500 bar only the zirconium or hafnium species of metallocenes may be used. Titanium species of metallocenes are generally unstable at such high pressure reactor conditions unless deposited upon a catalyst support.
A wide variety of Group IV B transition metal compounds have been named as possible candidates for an alumoxane cocatalyzed catalyst system. Although bis(cyclopentadienyl) Group IV B transition metal compounds have been the most preferred and heavily investigated for use in an alumoxane activated catalyst systems for polyolefin production, suggestions have appeared that mono and tris(cyclopentadienyl) transition metal compounds may also be useful. See, for example U.S. Pat. Nos. 4,522,982; 4,530,914 and 4,701,431. Such mono(cyclopentadienyl) transition metal compounds as are suggested as candidates for an alumoxane activated catalyst system are mono(cyclopentadienyl) transition metal trihalides and trialkyls.
More recently, International Publication No. WO 87/03887 described the use of a composition comprising a transition metal coordinated to at least one cyclopentadienyl and at least one heteroatom ligand as a transition metal component for use in an alumoxane activated catalyst system for .alpha.-olefin polymerization. The composition is broadly defined as a transition metal, preferably of Group IV B of the Periodic Table, which is coordinated with at least one cyclopentadienyl ligand and one to three heteroatom ligands, the balance of the transition metal coordination requirement being satisfied with cyclopentadienyl or hydrocarbyl ligands. Catalyst systems described by this reference are illustrated solely with reference to transition metal compounds which are metallocenes, i.e., bis(cyclopentadienyl) Group IV B transition metal compounds.
Even more recently, at the Third Chemical Congress of North American held in Toronto, Canada in June 1988, John Bercaw reported upon efforts to use a compound of a Group III B transition metal coordinated to a single cyclopentadienyl heteroatom bridged ligand as a catalyst system for the polymerization of olefins. Although some catalytic activity was observed under the conditions employed, the degree of activity and the properties observed in the resulting polymer product were discouraging of a belief that such monocyclopentadienyl transition metal compound could be usefully employed for commercial polymerization processes.
U.S. Pat. No. 4,931,517 discloses a process for the polymerization of ethylene which comprises bringing ethylene, or ethylene and at least one .alpha.-olefin in contact with a catalyst comprising a metallocene compound of a transition metal selected from Groups IV B, V B and VI B, an alumoxane and a silicon compound having a Si-O-C bond for polymerization. The use of the silicon compound by the '517 patent results in the production of ethylene polymers having a lower melt flow rate due to the reduced content of the low-molecular weight matters produced.
U.S. patent application Ser. No. 406,945, now abandoned; Ser. No. 533,245, now U.S. Pat. No. 5,055,438; and Ser. No. 581,841, now U.S. Pat. No. 5,096,867 (commonly owned) and, more recently European Patent Application 416815A2 describe an alumoxane activated catalyst system for olefin polymerization wherein the transition metal component comprises a Group IV B metal atom coordinated to a single cyclopentadienyl ligand, at least one heteroatom containing ligand wherein the heteroatom and cyclopentadienyl ligand may be (and in EPO 416815A2 must be) bridged together through a bridging group containing a Group IVA or VA element, and the balance of the valence of the transition metal atom comprises univalent anionic ligands.
A need still exists for discovering catalyst systems and polymerization processes that permit the production of higher molecular weight polyolefins and desirably with a narrow molecular weight distribution. Desirably such catalyst systems should be of high activity and productivity. It is further desirable that a catalyst be discovered which, within reasonable ranges of ethylene to .alpha.-olefin monomer ratios, will catalyze the incorporation of higher contents of .alpha.-olefin comonomers in the production of ethylene-.alpha.-olefins copolymers.